Classifications

• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M8/00—Fuel cells; Manufacture thereof
  • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
  • B01J41/08—Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
  • B01J41/12—Macromolecular compounds
  • B01J41/16—Cellulose or wood; Derivatives thereof
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J47/00—Ion-exchange processes in general; Apparatus therefor
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J47/00—Ion-exchange processes in general; Apparatus therefor
  • B01J47/016—Modification or after-treatment of ion-exchangers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/20—Manufacture of shaped structures of ion-exchange resins
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
  • C09K5/08—Materials not undergoing a change of physical state when used
  • C09K5/10—Liquid materials
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
  • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
  • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
  • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
  • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
  • C23F11/14—Nitrogen-containing compounds
  • C23F11/149—Heterocyclic compounds containing nitrogen as hetero atom
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
  • F01P—COOLING OF MACHINES OR ENGINES IN GENERAL; COOLING OF INTERNAL-COMBUSTION ENGINES
  • F01P11/00—Component parts, details, or accessories not provided for in, or of interest apart from, groups F01P1/00 - F01P9/00
  • F01P11/14—Indicating devices; Other safety devices
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M8/00—Fuel cells; Manufacture thereof
  • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
  • H01M8/04007—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids related to heat exchange
  • H01M8/04029—Heat exchange using liquids
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
  • F01P—COOLING OF MACHINES OR ENGINES IN GENERAL; COOLING OF INTERNAL-COMBUSTION ENGINES
  • F01P11/00—Component parts, details, or accessories not provided for in, or of interest apart from, groups F01P1/00 - F01P9/00
  • F01P11/06—Cleaning; Combating corrosion
  • F01P2011/066—Combating corrosion
  • F01P2011/068—Combating corrosion chemically
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/30—Hydrogen technology
  • Y02E60/50—Fuel cells
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
  • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

• the invention relates to pre-treated ion exchange resins, especially a corrosion inhibitor treated ion exchange resins and their use in heat transfer systems, alternative power sources such as fuel cells, and assemblies comprising such power sources.
• Heat transfer systems in thermal communication with a power source have been utilized to regulate heat generated during the operation of the power source.
• automotive vehicles have employed heat transfer fluids and cooling systems that transfer and dissipate heat generated as a by-product of gasoline powered internal combustion engines.
• the heat transfer fluids and cooling systems ensure that the engine operates in an optimum environment and is not subject to undesirably high temperatures.
• Fuel cells are a particularly attractive alternative power source because of their clean and efficient operation. Fuel cells have been proposed for use in numerous applications.
• fuel cells replace the internal combustion engines currently used in automobiles.
• fuel cells include Proton Exchange Membrane or Polymer Electrolyte Membrane (PEM) fuel cells, phosphoric acid (PA) fuel cells, molten carbonate (MC) fuel cells, solid oxide (SO) fuel cells, and alkaline fuel cells.
• PEM Proton Exchange Membrane or Polymer Electrolyte Membrane
• PA phosphoric acid
• MC molten carbonate
• SO solid oxide
• alkaline fuel cells alkaline fuel cells.
• a fuel cell assembly typically comprises an anode, a cathode, and an electrolyte in between the two electrodes.
• an oxidation reaction e.g., H 2
• the normal operating temperature of a PEM fuel cell assembly is controlled so that it remains within a range of from 60° C to 95°C. Because of the exothermic nature of the electrochemical reactions, it is desirable to use a heat transfer fluid or heat transfer fluid to keep the electrode assembly at an operating temperature that is within the desired operating temperature range. However, the presence of an electrical charge makes it challenging to use fuel cells with prior art heat transfer systems and fluids.
• a fuel cell based automotive engine might have many fuel cells connected together in series to form a fuel cell stack.
• Individual fuel cells may have an operating voltage of from 0.6 to 1.0V DC. In one instance, it is contemplated that anywhere from 100 to 600 individual fuel cells might be connected in series. As a result, the DC electrical voltage across automotive fuel cell stacks could be very high, typically ranging from 125 to 450 V DC.
• heat transfer fluids used with alternative power sources must also have high heat capacity, low viscosity, and high thermal conductivity. Such properties help minimize pressure drops and reduce pumping power requirements while still meeting heat transfer requirements.
• Good surface wetting properties are also desirable in a heat transfer fluid employed with alternative power sources. A heat transfer fluid with good surface wetting characteristics is helpful in reducing pressure drops at a condition of constant flow rate.
• Another important characteristic of a desirable heat transfer fluid is corrosion resistance. Many heat transfer fluid systems used with alternative power sources often have several metallic components. Illustrative metals found in heat transfer systems employed with alternative power sources include ferrous and non ferrous alloys such as stainless steel, aluminum, brass, braze alloy, and the like. However, such metals are vulnerable to corrosion as a result of contact with the heat transfer fluid.
• CA 2 435 593 discloses a method for deionizing a heat transfer medium of a fuel cell utilizing a two heat transfer circuit arrangement and a deionization cell wherein a diluate flows in one heat transfer circuit flowing through a fuel cell stack and a concentrate flow can be part of a secondary heat transfer circuit.
• Fuel cell coolants must also have high heat capacity, low viscosity, and high thermal conductivity. Such properties help minimize pressure drops and reduce pumping power requirements while still meeting heat transfer requirements. Good surface wetting properties are also desirable in a fuel cell coolant. A heat transfer fluid with good surface wetting characteristics is helpful in reducing pressure drops at a condition of constant flow rate.
• Heat transfer systems often have several metallic components.
• Illustrative metals found in fuel cell cooling systems and other heat transfer systems include ferrous and non ferrous alloys such as stainless steel, aluminum, brass, braze alloy, and the like. However, such metals are vulnerable to corrosion as a result of contact with the heat transfer fluid.
• corrosion inhibitors previously known for use in internal combustion engine coolants are unsuitable for use in fuel cell heat transfer fluids because they are typically highly conductive ionic species.
• Illustrative examples of such corrosion inhibitors are silicates, nitrites, molybdates, nitrates, carboxylates, phosphates, borates, and the like.
• Such ionic corrosion inhibitors cannot be used in fuel cell heat transfer fluids because of the requirement that fuel cell heat transfer fluids have very low conductivity.
• One major drawback of ion exchange resins or electrodeionization cell methods is that they may remove corrosion inhibitors. As a result, the fuel cell heat transfer fluid may lose its ability to inhibit the corrosion of metal components of the fuel cell heat transfer system.
• a pretreated ion exchange resin a method of maintaining low conductivity in a heat transfer fluid, an assembly, a heat transfer system, a fuel cell system, a method of maintaining low conductivity in corrosion inhibiting heat transfer fluid and a method of making a pretreated ion exchange resin.
• the pre-treated ion exchange resin comprises at least 15% by total number of exchangeable groups comprising at least one of an ion, a Lewis acid, or a Lewis base, resulting from a heat transfer fluid component having a pK a or pK b of greater than 5 in an aqueous solution at 25 0 C, based on the total number of exchangeable groups.
• suitable heat transfer fluid components include colorants, corrosion inhibitors, defoamers and/or anti-foaming agents, bitterants, dispersants, or a combination thereof.
• suitable heat transfer fluid components will have a pK a or pK b of from 5 to 14 in an aqueous solution at 25 0 C.
• the heat transfer fluid component will be a corrosion inhibitor.
• a corrosion inhibitor treated ion exchange resin is disclosed that comprises at least 15% of exchangeable groups comprising a corrosion inhibitor, based on the total number of exchangeable groups.
• the disclosed assembly is powered by an alternative power source and comprises an alternative power source and a heat transfer system in thermal communication with the alternative power source, the heat transfer system comprising a circulation loop defining a flow path for a heat transfer fluid having a conductivity of less than 200 ⁇ S/cm, and an ion exchange resin positioned in the flow path, the ion exchange resin comprising ion exchangeable groups, wherein at least 15% of the total ion exchangeable groups comprise either an ion, or a Lewis acid, or a Lewis base resulting from a heat transfer fluid component having a pKa or pK b of greater than 5 in an aqueous solution at 25 0 C, based on the total number of exchangeable groups.
• the alternative power source comprises an alternative power source and a heat transfer system in thermal
• the disclosed heat transfer system comprises a circulation loop defining a flow path for a heat transfer fluid having a conductivity of less than 200 ⁇ S/cm, and an ion exchange resin positioned in the flow path, the ion exchange resin having at least 15% of exchangeable groups comprising either an ion, or a Lewis acid, or a Lewis base resulting from a heat transfer fluid component having a pK a or pK b of greater than 5 in an aqueous solution at 25 0 C, based on the total number of exchangeable groups.
• the disclosed method of maintaining a conductivity of less than 200 ⁇ S/cm in a corrosion inhibiting heat transfer fluid comprises passing a heat transfer fluid through a heat transfer system, wherein the heat transfer fluid has a conductivity of less than 200 ⁇ S/cm and the heat transfer system comprises a circulation loop defining a flow path for the heat transfer fluid, and an ion exchange resin positioned in the flow path, the ion exchange resin comprising at least 15% of exchangeable groups comprising either an ion, or a Lewis acid, or a Lewis base resulting from a heat transfer fluid component having a pK a or pKb of greater than 5 in an aqueous solution at 25°C, based on the total number of exchangeable groups.
• the heat transfer fluid component is at least one of a colorant, a corrosion inhibitor, an anti-foaming agent, a bitterant, a dispersant, or a combination thereof.
• the heat transfer fluid component comprises a heat transfer fluid corrosion inhibitor.
• a method of making a treated ion exchange resin comprising contacting an ion exchange resin with an aqueous treatment solution comprising a heat transfer fluid component having a pK a or pK b of greater than 5 in an aqueous solution at 25 0 C, for a period of time sufficient to exchange at least 15% of the exchangeable sites with the heat transfer fluid component.
• the heat transfer fluid component is at least one of a colorant, a corrosion inhibitor, a bitterant, a dispersant, or a combination thereof.
• the heat transfer fluid component comprises a heat transfer fluid corrosion inhibitor.
• a fuel cell system comprising at least one fuel cell comprising an anode, a cathode, and an electrolyte; and a heat transfer system in thermal communication with the at least one fuel cell, comprising a circulation loop defining a flow path for a heat transfer fluid having a conductivity of less than 200 ⁇ S/cm, and an ion exchange resin positioned in the flow path, the ion exchange resin comprising at least 15% by total number of exchangeable groups comprising either an ion, or a Lewis acid, or a Lewis base resulting from a heat transfer fluid component having a pK a or pK b of greater than 5 in an aqueous solution at 25 0 C, based on the total number of exchangeable groups.
• the heat transfer fluid component is at least one of a colorant, a corrosion inhibitor, an anti-foaming agent, a bitterant, a dispersant, or a combination thereof.
• the heat transfer fluid component comprises a heat transfer fluid corrosion inhibitor.
• Figure 1 is a schematic diagram of one embodiment of the disclosed heat transfer system and fuel cell system.
• Figure 2 is a graph illustrating experimental results, showing the measured heat transfer fluid conductivity versus time in a simulated fuel cell cooling system test without the presence of ion exchange resin.
• Figure 3 is graph illustrating experimental results of another example, showing the measured heater transfer fluid conductivity versus time in a simulated fuel cell cooling system test, where a filter containing 150g Amberlite MB-150 mixed bed resin in the flow loop was used.
• Figure 4 is graph illustrating experimental results of another example, showing the measured conductivity versus time in a simulated fuel cell cooling system test, where a filter containing 6Og Dow strong acid cation ion exchange resin in the flow loop was used.
• Figure 5 is graph illustrating experimental results of another example, showing that the measured conductivity versus time in a beaker test, where 0.6g of a SYBRON strong base anion resin was added into lOOg of a heat transfer fluid for fuel cell cooling system.
• Figure 6 is a graph illustrating the ability of the disclosed pre-treated ion exchange resins to remove an ionic species from a heat transfer fluid.
• Figure 7 is a polarization curve measurement results illustrating the effect of the disclosed pre-treated ion exchange resins upon corrosion protection of metal sample.
• Figure 8 is a schematic diagram of an illustrative assembly comprising an alternative power source and a heat transfer system, more particularly a hybrid vehicle cooling system.
• the disclosed heat transfer fluids are suitable for use in assemblies comprising alternative power sources, especially fuel cells, and may be characterized as having very low conductivity.
• 'heat transfer fluid' refers to a fluid that is capable of transferring and dissipating a quantity of thermal energy from a first point to second point.
• the disclosed heat transfer fluids may be referred to as coolants.
• the disclosed heat transfer fluids may also be referred to as antifreeze, due to the ability of some heat transfer fluids to function as freezing point depressants.
• 'Heat transfer fluid' as used herein also refers to both concentrated solutions of the corrosion inhibitor and alcohol or water/alcohol mixtures as well as to diluted solutions of the same mixed with water, preferably deionized water.
• heat transfer fluid may be purchased, transported or used in concentrated solutions consisting mainly of one or more alcohols and corrosion inhibitor, such concentrates will often be diluted with water, especially deionized water, prior to incorporation or use in a fuel cell. Dilution ratios of from 1 :3 to 3:1 (DI water: Heat transfer fluid) are typical, with ratios of from 40%:60% to 60%:40% being used in one exemplary embodiment.
• DI water Heat transfer fluid
• the term 'heat transfer fluid' as used herein refers to both concentrated solutions and dilute solutions of the disclosed heat transfer fluids.
• the term 'low conductivity' as used herein generally refers to electrical conductivities of no more than 200 ⁇ S/cm.
• suitable heat transfer fluids will have a conductivity of less than 150 ⁇ S/cm, while in another embodiment, the suitable heat transfer fluids will have a conductivity of less than 50 ⁇ S/cm.
• suitable heat transfer fluids will have an electrical conductivity of from .02 ⁇ S/cm to no more than 200 ⁇ S/cm.
• the disclosed heat transfer fluids for use in fuel cells will have a conductivity of from 0.2 ⁇ S/cm to 100 ⁇ S/cm.
• the disclosed heat transfer fluids will have a conductivity of from 0.05 to less than 50 ⁇ S/cm, while in one exemplary embodiment, the disclosed heat transfer fluids will have a conductivity of from 0.05 to no more than 25 ⁇ S/cm.
• the disclosed heat transfer fluids will have an electrical conductivity of from 0.05 to no more than 10 ⁇ S/cm.
• the disclosed heat transfer fluids will have an electrical conductivity of from 0.05 to no more than 5 ⁇ S/cm.
• the electrical conductivity of the disclosed heat transfer fluids may be measured by using the test methods described in ASTM Dl 125, i.e., "Standard Test Methods for Electrical Conductivity and Resistivity of Water” or an equivalent method.
• a 'corrosion inhibiting heat transfer fluid' as used herein refers to a heat transfer fluid having a sufficient amount of one or more corrosion inhibitors such that metallic components immersed in said fluid have a reduced rate of corrosion relative to their corrosion in a heat transfer fluid that is identical in all respects except that it lacks any corrosion inhibitors.
• a pre-treated ion exchange resin a heat transfer system using said pre-treated ion exchange resin, an assembly using said heat transfer system, a fuel cell system using said heat transfer system and a method of using said pre-treated ion exchange resin to maintain low conductivity in a heat transfer fluid.
• Disclosed in another embodiment is a corrosion inhibitor treated ion exchange resin, a heat transfer system using said resin, an assembly using said heat transfer system, a fuel cell system using said heat transfer system, and a method of maintaining low conductivity in a corrosion inhibiting fuel cell heat transfer fluid.
• the disclosed pre-treated ion exchange resin comprises at least 15% by total number of exchangeable groups comprising either an ion, or a Lewis acid, or a Lewis base resulting from a heat transfer fluid component having a pK a or pK b of greater than 5 in an aqueous solution at 25 0 C, based on the total number of exchangeable groups.
• Suitable heat transfer fluid components that may be used to make the pre-treated resin include all components of a heat transfer fluid or heat transfer liquid that form a ionic species in an aqueous solution at 25 0 C.
• suitable heat transfer fluid components will have a pK a or pK b of from 5 to 14 in an aqueous solution at 25 0 C.
• suitable heat transfer fluid components will have a pK a or pK b of from 5 to less than 14 in an aqueous solution at 25 0 C.
• suitable heat transfer fluid components include colorants, corrosion inhibitors, antifoaming agents, bitterants, dispersants, or a combination thereof.
• the heat transfer fluid component present in the pre-treated resin will be at least one of a corrosion inhibitor, a colorant, or a combination thereof.
• the heat transfer fluid component present in the pre-treated resin will be a corrosion inhibitor.
• a pre-treated ion exchange resin such as a corrosion inhibitor treated ion exchange resin results from the pretreatment of ion exchange resins with one or more treatment heat transfer fluid components as described above.
• the heat transfer fluid component is a treatment corrosion inhibitor.
• the disclosed corrosion inhibitor treated ion exchange resins may be made by contacting an ion exchange resin with an aqueous treatment solution containing one or more treatment components such as corrosion inhibitors.
• the treatment results in the exchange of a treatment component such as an inhibitor with at least some of the exchangeable groups in the ion exchangeable resin.
• Suitable ion exchange resins include anion exchange resins, cation exchange resins, mixed bed ion exchange resins, and mixtures thereof.
• the particular ion exchange resin selected is dependent upon the type of heat transfer fluid component used in the heat transfer fluid.
• the particular ion exchange resin selected is dependent upon the type of corrosion inhibitor used in the heat transfer fluid.
• 'corrosion inhibitor' is used in the discussion below, it will be appreciated that it is merely illustrative of one type of heat transfer fluid component suitable for use in making and obtaining a treated ion exchange resin.
• the ion exchange resins suitable for use in making any of the pre- treated ion exchange resins disclosed herein will generally have a polymer matrix and functional groups 'paired' with an exchangeable ion form.
• the exchangeable ion form is generally one or more of Na+, H+, OH " , or CI ' ions, depending on the type of ion exchangeable resin. These exchangeable ions exchange with the ionic species produced by the one or more corrosion inhibitors present in an aqueous corrosion inhibitor treatment solution. These exchangeable ions exchange with any ionic species produced by the one or more corrosion inhibitors present in an aqueous inhibitor treatment solution and in some cases with the ionic inhibitor species present in a corrosion inhibiting fuel cell heat transfer fluid.
• a heat transfer fluid component such as a corrosion inhibitor becomes a negatively charged species in solution, i.e., for example if N- heterocyclic compounds are used as a corrosion inhibitor
• the ion exchange resin should be a mixed bed resin, an anion exchange resin, or a mixture thereof.
• commercially available anion exchange resins are typically in either OH * or Cl " forms. In one exemplary embodiment, a selected anion exchange resin will be in the OH " form.
• a heat transfer fluid component such as a corrosion inhibitor in a corrosion inhibiting heat transfer fluid becomes a positively charged species in solution
• mixed bed resins, cation exchange resins or a mixture thereof should be used.
• Commercially available cation exchange resins are typically in either H + or Na + forms. In one exemplary embodiment, a selected cation exchange resin will be in the H + form.
• ion exchange resins in Na + or Cl " forms will be used only if the treatment with an aqueous component solution such as an aqueous corrosion inhibitor solution results in the removal of substantially all of the Na + or Cl " ions from the ion exchange resin.
• ion exchange resins in Na+ or Cl " forms will be used only if the treatment with the aqueous component solution results in the production of a corrosion inhibitor treated ion exchange resin having at least 90% of exchangeable groups comprising a suitable heat transfer fluid component such as a corrosion inhibitor.
• polystyrene, polystyrene and styrene copolymers examples include polystyrene, polystyrene and styrene copolymers, polyacrylate, aromatic substituted vinyl copolymers, polymethacrylate, phenol-formaldehyde, polyalkylamine, combinations thereof, and the like.
• the polymer matrix will be polystyrene and styrene copolymers, polyacrylate, or polymethacrylate, while in one exemplary embodiment; the polymer matrix will be styrene divinylbenzene copolymers.
• Examples of illustrative functional groups in cation ion exchange resins include sulfonic acid groups (-SO 3 H), phosphonic acid groups (-PO 3 H), phosphinic acid groups (-PO 2 H), carboxylic acid groups (-COOH or -C(CH 3 )- COOH), combinations thereof, and the like.
• the functional groups in a cation exchange resin will be -SO 3 H, -PO 3 H, or -COOH, while in one exemplary embodiment; the functional groups in a cation exchange resin will be - SO 3 H.
• Examples of illustrative functional groups in anion exchange resins include quaternary ammonium groups, e.g., benzyltrimethylammonium groups (also termed type 1 resins), benzyldimethylethanolammonium groups (also termed type 2 resins), trialkylbenzyl ammonium groups (also termed type 1 resins); or tertiary amine functional groups, and the like.
• the functional groups in an anion exchange resin will be trialkylbenzyl ammonium, trimethylbenzyl ammonium, or dimethyl-2-hydroxyethylbenzyl ammonium, while in one exemplary embodiment; the functional groups in an anion exchange resin will be trialkylbenzyl ammonium.
• ion exchange resins suitable for use herein are available from Rohm & Haas of Philadelphia, PA. as AmberliteTM, AmberjetTM, DuoliteTM, and ImacTM resins, from Bayer of Leverkusen, Germany as LewatitTM resin, from Dow Chemical of Midland, MI as DowexTM resin, from Mitsubishi Chemical of Tokyo, Japan as DiaionTM and ReliteTM resins, from Purolite of BaIa Cynwyd, PA as PuroliteTM resin, from Sybron of Birmingham, NJ as IonacTM resin, from Resintech of West Berlin, NJ, and the like.
• a suitable commercially available ion exchange resin will be DowexTM MR-3 LC NG Mix mixed bed resin, DowexTM MR-450 UPW mixed bed resin, Sybron IonacTM NM-60 mixed bed resin, or AmberliteTM MB-150 mixed bed resin, while in one exemplary embodiment, a suitable commercially available ion exchange resin will be DowexTM MR-3 LC NG Mix.
• the ion exchange resin is contacted with an aqueous treatment solution comprising a suitable heat transfer fluid component such as a corrosion inhibitor. It will be appreciated that other components such as described herein are also suitable for use.
• a suitable heat transfer fluid component may be referred to as a 'treatment component'.
• Suitable heat transfer fluid components that may be used to make the pre-treated resin include all components of a heat transfer fluid or heat transfer liquid that form either an ionic species or a Lewis acid or a Lewis base in an aqueous solution at 25 0 C.
• suitable heat transfer fluid components will have a pK a or pK b of from 5 to 14 in an aqueous solution at 25 0 C.
• suitable heat transfer fluid components will have a pK a or pK b of from 5 to less than 14 in an aqueous solution at 25 0 C.
• a suitable treatment heat transfer fluid component is a 'treatment corrosion inhibitor' or 'treatment inhibitor'.
• Suitable treatment inhibitors for use in the aqueous treatment solution of inhibitor include weakly ionic corrosion inhibitors that are soluble or dispersible in an alcohol or in a mixture of one or more alcohols and water.
• Corrosion inhibitors suitable for use as treatment inhibitors in one embodiment will have a pK a value of equal to or greater than 5 if it is an acid in an aqueous solution at 25 0 C.
• suitable treatment inhibitors will have a pK a value of from 5 to 14.
• suitable acid treatment inhibitors will have a pK a value of from 5 to less than 14.
• a treatment inhibitor is a base
• the pK b value of suitable treatment inhibitors should be equal to or greater than 5 in an aqueous solution at 25 0 C.
• suitable basic treatment inhibitors will have a pK b value of from 5 to 14.
• a suitable basic treatment inhibitor will have a pK b value of from 5 to less than 14.
• suitable treatment inhibitors will possess good stability in a mixture of alcohol and water under fuel cell operating conditions, i.e., typically temperatures of from about 40 0 C to about 100 0 C.
• a treatment component such as a treatment inhibitor will comprise at least some minimum number of functional groups that will form an ionic species due to hydrolysis in an aqueous alcohol or alkylene glycol solution.
• the treatment inhibitor may comprise from 1 to 10 number of ionic forming functional group per molecule, more preferably from 1 to 5 per molecule of treatment inhibitor.
• Illustrative ionic forming functional groups are those selected from the group consisting of amine groups, heterocyclic aromatic groups, and other N-containing groups, and phenol or naphthol derivatives.
• the treatment inhibitor will comprise an azole compound.
• Suitable azole compounds are five-membered heterocyclic compounds having 1 to 4 nitrogen atoms.
• Illustrative examples include imidazoles, triazoles, thiazoles and tetrazoles of the formulas (I), (II), (III) and (IV) below, such as benzotriazole, tolytriazole, alkyl benzotriazoles, such as 4-methyl benzotriazole, 5- methyl benzotriazole, and butyl benzotriazole and the like, benzimidazole, halobenzotriazoles, such as chloro-methylbenzotriazole, tetrazole, substutited tetrazoles, thiazoles, such as 2-mercaptobenzothiazole, and the like.
• the azole compound will be of the formula (I), (II), (III) or (IV):
• R is hydrogen or halogen such as Cl or Br, or a Ci to C 20 alkyl group; R' is at least one of hydrogen, Ci to C 20 alkyl group, or SH or SR group; and X is N, C-SH or CH; and Y is selected from N, C-R or CH group, and R is defined as above.
• the azole compound will be of formula (I) wherein X is N.
• the azole compound will be of formula (I) wherein X is N and R is hydrogen or an alkyl group of from 1 to less than 10 carbons.
• alkyl includes both branched and straight chain saturated aliphatic hydrocarbon groups, having the specified number of carbon atoms.
• Ci-C 7 alkyl indicates an alkyl group having from 1 to about 7 carbon atoms.
• heterocycloalkyl(Co-C 2 alkyl) the indicated group, in this case heterocycloalkyl, is either directly bound by a single covalent bond (C 0 ), or attached by an alkyl chain having the specified number of carbon atoms, in this case from 1 to about 2 carbon atoms.
• alkyl examples include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, 3-methylbutyl, t-butyl, n-pentyl, and sec-pentyl.
• Suitable azole compounds include benzotriazole, tolytriazole, methyl benzotriazole, i.e., 4-methyl benzotriazole and 5- methyl benzotriazole, butyl benzotriazole, mercaptobenzothiazole, benzimidazole, halo-benzotriazoles, such as chloro-methylbenzotriazoles, and the like.
• the azole compound will be one of benzotriazole, tolytriazole, or mercaptobenzothiazole, while in one exemplary embodiment; the azole compound will be benzotriazole.
• the aqueous inhibitor solution used to make the corrosion inhibitor treated ion exchange resins will generally have a concentration of treatment inhibitor as described above of at least 1000 ppm at a temperature of greater than ⁇ 2 degrees C. In one embodiment, the aqueous inhibitor solution will have a concentration of from 0.001% to 90% by weight, while in another embodiment; the aqueous inhibitor solution will have a concentration of from 0.005% to 10% by weight.
• the aqueous inhibitor solutions will be made with deionized water.
• the ion exchange resin is contacted with the aqueous component solution for a period of time sufficient to allow the treatment component such as a treatment inhibitor to exchange places with at least 15% of the total exchangeable groups, based on the total number of exchangeable ions in the ion exchange resin. That is, in one embodiment, the inhibitor loading of the corrosion inhibitor treated ion exchange resin should be at least 15% of the exchange capacity of the ion exchange resin. In another embodiment, the period of contact is sufficient to allow the treatment inhibitor to exchange places with at least 50% of the total exchangeable groups, based on the total number of exchangeable ions in the ion exchange resin.
• the period of contact is sufficient to allow the treatment inhibitor to exchange places with at least 75% of the total exchangeable groups, based on the total number of exchangeable ions in the ion exchange resin. In another exemplary embodiment, the period of contact is sufficient to allow the corrosion inhibitor loading to be an amount of from 15 to 99% of the total exchange capacity of the resin or from 15 to 99% of the total exchangeable groups, based on the total number of exchangeable ions in the ion exchange resin.. [0080]
• the resultant pre-treated ion exchange resins, and in one exemplary embodiment, the corrosion inhibitor treated ion exchange resins will be cleansed with de-ionized water and/or clean fuel cell heat transfer fluid to minimize the chance for accidental introduction of impurities.
• the disclosed pre-treated ion exchange resins will be used in a heat transfer system, especially a fuel cell heat transfer system.
• a heat transfer system especially a fuel cell heat transfer system.
• the disclosed pre-treated ion exchange resins and heat transfer fluids passing through such resins to maintain low conductivity may be used in applications other than fuel cells that require a heat transfer liquid.
• Particularly suitable applications are those having heat transfer systems that require heat transfer fluids having low conductivity.
• Illustrative examples include glass and metal manufacturing processes where a high electrical voltage/current is applied to the electrodes used to keep a material such as glass or steel in a molten state. Such processes typically require a heat transfer fluid having low conductivity to cool the electrodes.
• the pre-treated ion exchange resins disclosed herein are suitable for use in such heat transfer systems.
• the disclosed corrosion inhibitor treated ion exchange resin will be used in a fuel cell heat transfer system.
• a suitable fuel cell heat transfer system 10 will comprise a circulation loop 12 that defines a flow path 14 that is in thermal communication with at least one fuel cell 16 comprising an anode 18, a cathode 20, and an electrolyte 22.
• the term 'thermal communication' as used herein refers to any arrangement that allows heat produced by the exothermic reaction in the fuel cell 16 to be transferred to the corrosion inhibiting heat transfer fluid by heat transfer.
• the flow path 14 will pass through a heat transfer fluid channel 26 in the fuel cell 16.
• a corrosion inhibitor treated ion exchange resin 28 is placed in flow path 14 so that corrosion inhibiting heat transfer fluid 24 must pass there through.
• corrosion inhibitor treated ion exchange resin 28 may be placed in a filter 30 that is placed in the flow path 14 of circulation loop 12.
• the heat transfer fluid channel 26 may be comprised of multiple channels or may be configured to wrap around the fuel cell 16.
• the heat transfer fluid channels should be in close proximity to the electrode assembly surfaces where oxidation reaction of the fuel(s) and/or the reduction reaction of the oxidant(s) are taking place, so that effective heat transfer between heat transfer fluid and the electrode assembly can be accomplished.
• the heat transfer fluid channels and the fuel and oxidant flow channels are generally mechanically isolated from each other, so that undesirable interference among fuel, oxidant and heat transfer fluid will not occur.
• the disclosed treated ion exchange resins and/or heat transfer fluids may be used in a variety of assemblies comprising one or more alternative power sources.
• the term 'alternative power source' as used here refers to power source technologies that provide improvements in energy efficiency, environmental concerns, waste production and management issues, natural resource management, and the like.
• Examples of alternative power sources that have been developed include, but are not limited to, batteries, fuel cells, solar cells or solar panels, photovoltaic cells, and internal combustion engines powered by the condensation of steam, natural gas, diesel, hydrogen, and/or the like.
• the term 'alternative power source' includes devices powered by internal combustion engines operating with a clean heat transfer system, i.e., a heat transfer system that does not contribute to the concentration of ionic species in the heat transfer fluid.
• Such alternative power sources may be used alone or in combinations thereof, such as those employed in hybrid vehicles.
• assemblies comprising such alternative power sources may include any article traditionally powered by an internal combustion engine, such as automotive vehicles, boats, generators, lights, aircrafts and airplanes, trains or locomotives, military transport vehicles, stationary engines, and the like.
• the assemblies also include additional systems or devices required for the proper utilization of alternative power sources, such as electric motors, DC/DC converters, DC/ AC inverters, electric generators, and other power electronic devices, and the like.
• the assemblies may also include systems or devices required for the proper utilization of the alternative power sources such as electric motors, DC/CC converters, DC/AC inverters, electric generators, and other power electronics and electrical devices, and the like.
• the disclosed assemblies will generally comprise an alternative power source and a heat transfer system in thermal communication with the alternative power source.
• the heat transfer system will comprise a circulation loop defining a flow path for a corrosion inhibiting heat transfer fluid having a conductivity of less than 200 ⁇ S/cm.
• the heat transfer system will comprise a circulation loop defining a flow path for a corrosion inhibiting liquid heat transfer fluid having a conductivity of less than 200 ⁇ S/cm and comprising a corrosion inhibitor comprising an azole compound, and at least one of a siloxane based surfactant, colloidal silica, or mixtures thereof.
• the assembly may contain internal combustion engine 5, or fuel cells 5 or solar cells 5 as the vehicle primary power source 7. It also contains a rechargeable secondary battery 12 or an optional ultra-capacitor 13 that may be charged via the vehicle regenerative braking system. In this embodiment, the battery 12 and/or the ultra-capacitor 13 may act as secondary power sources.
• the assembly may also contain power electronic devices, such as DC/DC converters 10, DC/AC inverters 10, generators 8, power splitting devices 9, and/or voltage boost converters 11, etc.
• the assembly may also contain fuel cell or solar cell "balance of plant" subsystems 6. These may be air compressors, pumps, power regulators, etc.
• the assembly also contain HAVC systems 14, e.g., air- conditioning system for the climate control of vehicle interior space. These are included in the vehicle system 16 in the illustrated assembly of Figure 1 that may require the use of coolant or heat transfer fluid for temperature control.
• the assembly in the illustrate example also contain a coolant recirculation pump 1, coolant flow path 4, coolant tank 2, and a radiator or heat exchanger 3, and a fan 15.
• the fan may be substituted by an external cooling source, e.g., a different (or isolated) cooling system with its own cooling media.
• the alternative power source will be a fuel cell. It will be appreciated that a fuel cell is in thermal communication with the disclosed heat transfer systems and fluids, the electrical conductivity of the disclosed heat transfer fluids will be, in one embodiment, no more than 10 uS/cm. In an especially exemplary embodiment comprising a fuel cell, the disclosed heat transfer fluids will have an electrical conductivity of from 0.02 to no more than 10 ⁇ S/cm. In one especially exemplary embodiment, the disclosed corrosion inhibiting heat transfer fluids will have an electrical conductivity of from 0.05 to no more than 5 ⁇ S/cm.
• the disclosed corrosion inhibiting heat transfer fluids may be used in a number of different types of fuel cells comprising an electrode assembly comprising an anode, a cathode, and an electrolyte, and a heat transfer fluid in thermal communication with the electrode assembly or fuel cell.
• the heat transfer fluid may be contained or flow in channel or flow path defined by a circulation loop or heat transfer fluid flow channel in thermal communication with said fuel cell.
• Illustrative types of suitable fuel cells include PEM (Proton Exchange
• the disclosed corrosion inhibiting heat transfer fluids will be used in PEM and AFC fuel cells.
• the disclosed heat transfer systems, assemblies, and fuel cell systems will employ suitable heat transfer fluids that may be characterized as having very low conductivity as defined above.
• suitable heat transfer fluids will comprise a heat transfer fluid inhibitor as described herein.
• suitable heat transfer fluids will comprise at least one alcohol in addition to the heat transfer fluid inhibitor.
• the corrosion inhibiting fuel cell heat transfer fluids will comprise a corrosion inhibitor, at least one alcohol, and water.
• the corrosion inhibiting fuel cell heat transfer fluids will comprise a corrosion inhibitor as disclosed herein, water, at least one alcohol, a colorant, and optionally one or more additives such as an antifoam agent, a bittering agent, a wetting agent, a non-ionic dispersant and the like.
• the heat transfer fluid used in the disclosed heat transfer systems, assemblies, and fuel cell systems will be a corrosion inhibiting heat transfer fluid that comprises at least one corrosion inhibitor.
• the corrosion inhibitor used in the corrosion inhibiting heat transfer fluid i.e., a 'heat transfer fluid inhibitor' may be the same or different with respect to the 'treatment inhibitor' used in the aqueous treatment solution as described above.
• the heat transfer fluid component used in the treatment solution will also be present as a component of the heat transfer fluid. However, in one exemplary embodiment, additional components will be present as part of the heat transfer fluid.
• At least one treatment inhibitor present in a corrosion inhibitor treated ion exchange resin will be the same as at least one heat transfer fluid corrosion inhibitor used in a corrosion inhibiting heat transfer fluid. In another embodiment, at least one treatment inhibitor present in a corrosion inhibitor treated ion exchange resin will be the same as at least one heat transfer fluid inhibitor used in a corrosion inhibiting heat transfer fluid that is used in a heat transfer system employing said corrosion inhibitor treated ion exchange resin. In one exemplary embodiment, the treatment inhibitors present in a corrosion inhibitor treated ion exchange resin will be the same as the heat transfer fluid inhibitors used in a heat transfer fluid used in a heat transfer system employing said corrosion inhibitor treated ion exchange resin.
• the corrosion inhibitor used in the treatment solution will also be present as the corrosion inhibitor of the heat transfer fluid.
• additional components will be present as part of the heat transfer fluid corrosion inhibitor.
• the heat transfer fluid inhibitor will comprise an azole compound and at least one of at least one of a siloxane based surfactant, colloidal silica or a mixture thereof.
• Suitable azole compounds are five-membered heterocyclic compounds having 1 to 4 nitrogen atoms.
• Illustrative examples include imidazoles, triazoles, thiazoles and tetrazoles of the formulas (I), (II), (III) and (IV) below, such as benzotriazole, tolytriazole, alkyl benzotriazoles, such as 4-methyl benzotriazole, 5- methyl benzotriazole, and butyl benzotriazole and the like, benzimidazole, renzenzotriazoles, such as chloro-methylbenzotriazole, tetrazole, substituted tetrazoles, thiazoles, such as 2-mercaptobenzothiazole, and the like.
• the azole compound will be of the formula (I), (II), (III) or (IV):
• R is hydrogen, or halogen such as Cl or Br, or a Ci to C 20 aliphatic or alkyl group
• R' is selected from hydrogen, Ci to C 20 aliphatic group, or SR or SH group
• X is selected from N (or nitrogen atom), C-SH or CH
• Y is selected from N (or nitrogen atom), C-R or CH group.
• the azole compound will be of formula (I) wherein X is N.
• the azole compound will be of formula (I) wherein X is N and R is hydrogen or an alkyl group of from 1 to less than 10 carbons.
• alkyl includes both branched and straight chain saturated aliphatic hydrocarbon groups, having the specified number of carbon atoms.
• Ci-C 7 alkyl indicates an alkyl group having from 1 to about 7 carbon atoms.
• heterocycloalkyl(Co-C 2 alkyl) the indicated group, in this case heterocycloalkyl, is either directly bound by a single covalent bond (Co), or attached by an alkyl chain having the specified number of carbon atoms, in this case from 1 to about 2 carbon atoms.
• alkyl examples include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, 3-methylbutyl, t-butyl, n-pentyl, and sec- pentyl.
• suitable azole compounds include benzotriazole, tolytriazole, methyl benzotriazole, i.e., 4-methyl benzotriazole and 5- methyl benzotriazole, butyl benzotriazole, mercaptobenzothiazole, benzimidazole, halo-benzotriazoles, such as chloro-methylbenzotriazoles, and the like.
• the azole compound will be one of benzotriazole, tolytriazole, or mercaptobenzothiazole, while in one exemplary embodiment, the azole compound will be benzotriazole.
• the azole compound may be present in the corrosion inhibiting heat transfer fluid in an amount of from 1 ppm to about 5000 ppm, while in one exemplary embodiment; the azole compound will be present in an amount of from 10 ppm to about 500 ppm, based on the total weight of the heat transfer fluid.
• the azole compound used in the inhibitor treatment solution will be the same as an azole compound used in the corrosion inhibitor of the fuel cell heat transfer fluid.
• the corrosion inhibitor for a fuel cell heat transfer fluid will also have at least one of a siloxane based surfactant, colloidal silica or a mixture thereof.
• Siloxane based surfactants as used herein generally refers to polysiloxanes and organosilane compounds comprising at least one silicon-carbon bond.
• suitable polysiloxanes are generally those polysiloxanes believed to be of the general formula R" 3 -Si-[O-Si(R") 2 ] x -OsiR" 3 wherein R" is an alkyl group or polyalkylene oxide copolymer of from 1 to 200 carbons and x can be from 0 to 100.
• suitable polysiloxanes will have at least one R" group that is a hydrophilic group such as a polyalkylene oxide copolymer of one or more alkylene oxides having from 2 to 6 carbons, especially from 2 to 4 carbons.
• suitable polysiloxanes may be defined by similarities to suitable commercially available polysiloxanes such as the Silwet® siloxane surfactants from GE Silicones/OSi Specialities, and other similar siloxane-polyether copolymers available from Dow Corning or other suppliers.
• suitable siloxane based surfactants will be exemplified by Silwet® L-77, Silwet® L-7650, Silwet® L-7600, Silwet® L-7657, Silwet® L- 7200, Silwet® L-7210, and the like.
• Suitable organosilane compounds are those silane compounds comprising at least one silicon-carbon bond capable of hydrolyzing in the presence of water to form a silanol, i.e., a compound with one or more Si-OH groups.
• suitable organosilane compounds are those of the general formula ZSi(OZ) 3 wherein the Z groups may be aromatic groups, cycloaliphatic groups, alkyl groups, alkoxy groups, or alkylene groups, and may contain heteroatoms such as N, S, or the like in the form of functional groups such as amino groups, epoxy groups, and the like.
• suitable organosilane compounds are of the general formula Z 5 Si(OZ) 3 wherein Z' may be at least one of aromatic groups, cycloaliphatic groups, alkyl groups, alkoxy groups, or alkylene groups, and may contain heteroatoms such as N, S, or the like in the form of functional groups such as amino groups, epoxy groups, and the like, while Z is an alkyl group of from 1 to 5 carbons.
• organosilanes for which the structure is unknown or which is outside the scope of this formula may also be suitable for use in the corrosion inhibitor of a fuel cell heat transfer fluid.
• suitable organosilanes may be defined by similarities to suitable commercially available organosilanes such as the Silquest® or Formasil® surfactants from GE Silicones/OSi Specialities, and other suppliers.
• siloxane based surfactants will be exemplified by Formasil 891, Formasil 593, formasil 433, Silquest Y-5560 silane (i.e., polyalkyleneoxidealkoxysilane), Silquest A-186 (2-(3,4- epoxycyclohexyl)ethyltrimethoxysilane), Silquest A-187 (3- glycidoxypropyltrimethoxysilane), or other Silquest silanes available from GE Silicones, Osi Specialties or other suppliers and the like.
• silane i.e., polyalkyleneoxidealkoxysilane
• Silquest A-186 (2-(3,4- epoxycyclohexyl)ethyltrimethoxysilane
• Silquest A-187 (3- glycidoxypropyltrimethoxysilane)
• Silquest silanes available from GE Silicones, Osi Specialties or other suppliers and the like.
• Suitable organosilanes which are believed to be commercially available and are illustrative of suitable siloxane based surfactants include 3-aminopropyltriethoxysilane, N-2-(aminoethyl)-3- aminopropyltrimethoxysilane, octyltriethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, methyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, isobutyltrimethoxysilane, phenyltrimethoxysilane, methyltrimethoxysilane, and other such siloxane based surfactants having similar structures but varying numbers of carbons.
• the siloxane based surfactant may be present in the corrosion inhibiting heat transfer fluid in an amount of from 0.01 wt% to about 10 wt%, based on the total weight of the heat transfer fluid, while in one exemplary embodiment; the siloxane based surfactant will be present in the corrosion inhibiting heat transfer fluid in an amount of from 0.02 wt% to about 2 wt%, based on the total weight of the heat transfer fluid.
• the corrosion inhibiting heat transfer fluid may also comprise silica.
• silica refers to either colloidal silica, silica in nano-form or a combination thereof.
• the terms 'colloidal silica' and 'silica' are used herein interchangeablely. While not wishing to be bound to a particular theory, it is believed that the use of colloidal silica of a particular average particle size provides improvements in heat transfer efficiency and/or the heat capacity of a fuel cell heat transfer fluid.
• suitable silica will have a nominal particle size of from about 1 nm to about 200 nm. In one exemplary embodiment suitable silica will have an average particle size of from about 1 nm to about 100 nm while in one especially exemplary embodiment, suitable silica will have an average particle size of from 1 nm to about 40 nm.
• Suitable silica having the appropriate particle size is commercially available under the Ludox® brand from DuPont or Grace Davidson, under the Nyacol® or Bindzil® brands from Akzo Nobel or Eka Chemicals, under the Snowtex® brand from Nissan Chemical.
• Other suppliers of suitable silica include Nalco and the like.
• the silica will be used in the corrosion inhibiting heat transfer fluid in an amount of no more than 10,000 ppm, while in one exemplary embodiment; the silica will be used in an amount of less than 2000 ppm.
• the corrosion inhibitor of the corrosion inhibiting heat transfer fluid may also comprise a combination of the siloxane based surfactant and silica.
• the corrosion inhibitor will comprise a combination of the azole compound and the disclosed siloxame compound.
• the corrosion inhibitor will consist of the azole and siloxane combination.
• the heat transfer fluid intended for use with the disclosed pre-treated ion exchange resins or in the disclosed heat transfer systems, assemblies, or fuel cell systems will also comprise a colorant.
• the heat transfer fluid will comprise a colorant that is a non-ionic or weakly ionic species that are soluble or dispersible in the at least one alcohol or a mixture of the disclosed alcohols and water.
• a suitable colorant will be a non-conductive colorant that is substantially free of functional groups that will form an ionic species due to hydrolysis in an aqueous alcohol or alkylene glycol solution.
• substantially free refers to an amount that is not in excess of an amount that will lead to the conductivity of the heat transfer fluid being higher than 5 ⁇ S/cm.
• the functional groups that will produce small amounts of ionic species include many N-containing compounds, e.g., acridine, amine, thiazole, cresol, etc. Compounds containing sulfonic acid groups, phosphonic acid groups, carboxylic acid groups, etc.
• a non-conductive heat transfer fluid colorant will substantially free of functional groups selected from the group consisting of carboxylate groups, sulfonate groups, phosphonate groups, quaternary ammonium cation groups, groups that carry a positive charge, and groups that carry a negative charge.
• functional groups selected from the group consisting of carboxylate groups, sulfonate groups, phosphonate groups, quaternary ammonium cation groups, groups that carry a positive charge, and groups that carry a negative charge.
• groups that carry a positive charge include Na + , Cu 2+ , N + (CH 3 ) 3 , Fe 3+ , combinations thereof, and the like.
• groups that carry a negative charge include Cl “ , Br " , SO 4 2" , combinations thereof, and the like.
• Suitable heat transfer fluid colorants may comprise at least one of the following chromophores: anthraquinone, triphenylmethane, diphenylmethane, azo containing compounds, disazo containing compounds, trisazo containing compounds, diazo containing compounds, xanthene, acridine, indene, phthalocyanine, azaannulene, nitroso, nitro, diarylmethane, triarylmethane, methine, indamine, azine, oxazine, thiazine, quinoline, indigoid, indophenol, lactone, aminoketone, hydroxyketone, stilbene, thiazole, one or more conjugated aromatic groups, one or more conjugated heterocyclic groups (e.g., stilkene, and or bestriazenylamino- stilkene, and/or pyrazoline, and/or coumarine type molecules or mixtures thereof), one or more conjugated carbon
• the heat transfer fluid colorant will comprise at least one of diarylmethane, triarylmethane, triphenylmethane, diphenylmethane, one or more conjugated aromatic groups, azo, or combinations thereof. In one especially exemplary embodiment, the heat transfer fluid colorant will comprise at least one or more conjugated aromatic groups as a chromophore. [00123] In another embodiment, the heat transfer fluid colorant will comprise the reaction product of a non-conductive alkoxy compounds and at least one chromophore such as described above. Illustrative examples of suitable non- conductive alkoxy compounds include those having from 1 to 30 carbons.
• Illustrative alkoxy compounds include ethylene oxide, propylene oxide, butylene oxide, and the like, with ethylene oxide and propylene oxide being particularly suitable.
• the chromophore reacted with the alcohol will be selected from the group consisting of anthraquinone, triphenylmethane, diphenylmethane, diarylmethane, triarylmethane, azo containing compounds, disazo containing compounds, trisazo containing compounds, diazo containing compounds, and combinations thereof.
• suitable heat transfer fluid colorants may be described as those colorants will be of the formula:
• R is an organic chromophore selected from the group consisting of anthraquinone, triphenylmethane, diphenylmethane, azo containing compounds, disazo containing compounds, trisazo containing compounds, diazo containing compounds, xanthene, acridine, indene, phthalocyanine, azaannulene, nitroso, nitro, diarylmethane, triarylmethane, methine, indamine, azine, oxazine, thiazine, quinoline, indigoid, indophenol, lactone, aminoketone, hydroxyketone, stilbene,.thiazole, two or more conjugated aromatic groups, two or more conjugated heterocyclic groups, or combinations thereof;
• A is a linking moiety in said chromophore and is selected from the group consisting of O, N or S; k is 0 or 1;
• suitable heat transfer fluid colorants are those colorants of the above formula wherein B is selected from the group of one or more alkyleneoxy constitutuents containing from 2 to 4 carbon atoms, n is from 1 to 30, m is 1 or 2, X is preferably 1 or 2, and R 1 is preferably H or a CpC 4 alkyl or alkoxy groups containing from 1 to 6 carbon atoms.
• suitable heat transfer fluid colorants are those containing one or more of diarylmethane, triarylmethane, triphenylmethane, diphenylmethane, conjugated aromatic groups or conjugated carbon-carbon double bonds or a combination thereof, since such are not expected to contribute to conductivity increase from the chromophore. In other words, these chromophore structures have no groups that will hydrolyze. Among the listed linking group, O may also be less likely to hydrolyze in aqueous solution. [00126]
• the heat transfer fluid colorants may be prepared by various known methods as are described above with respect to the treatment inhibitors.
• suitable heat transfer fluid colorants for use in corrosion inhibiting heat transfer fluids suitable for use in the disclosed fuel cells and fuel cell systems include Liquitint® Red ST or other similar polymeric colorants from Milliken Chemical of Spartanburg, SC, USA, or colorants (e.g., Liquitint® Blue RE) from Chromatech of Canton, MI, USA.
• illustrative colorants include the following: Liquitint Red ST, Liquitint Blue RE, Liquitint Red XC, Liquitint Patent Blue, Liquitint Bright yellow, Liquitint Bright orange, Liquitint Royal Blue, Liquitint Blue N-6, Liquitint Bright Blue, Liquitint Supra Blue, Liquitint Blue HP, Liquitint Blue DB, Liquitint Blue II, Liquitint Exp.
• Liquitint Yellow BL Liquitint Yellow II, Liquitint Sunbeam Yellow, Liquitint Supra yellow, Liquitint Green HMC, Liquitint violet, Liquitint Red BL, Liquitint Red RL, Liquitint Cherry Red, Liquitint Red II, Liquitint Teal, Liquitint Yellow LP, Liquitint Violet LS, Liquitint Crimson, Liquitint Aquamarine, Liquitint Green HMC, Liquitint Red HN, Liquitint Red ST, as well as combinations thereof.
• the heat transfer fluid colorant will be at least one of Liquitint® Red ST from Milliken, Liquitint® Red XC from Chromatech, Liquitint® Patent Blue from Milliken, Chromatint® Yellow 1382 from Chromatech or Liquitint® Blue® RE from Chromatech, while in an especially exemplary embodiment, the non-conductive colorant will be Liquitint® Blue RE from Chromatech.
• the heat transfer fluid colorant will be present in the corrosion inhibiting heat transfer fluid in an amount of from 0.0001 to 0.2% by weight, based on the total amount of the corrosion inhibiting heat transfer fluid. In another embodiment, the heat transfer fluid colorant will be present in the heat transfer fluid in an amount of from 0.0005-0.1% by weight, based on the total amount of the heat transfer fluid, while in one exemplary embodiment, the heat transfer fluid colorant will be used in an amount of from 0.0005 to 0.05% by weight, based on the total amount of the heat transfer fluid.
• suitable alcohols for use in the disclosed heat transfer fluids are methanol, ethanol, propanol, butanol, furfural, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3- propylene glycol, dipropylene glycol, butylene glycol, glycrol, monoethylether of glycerol, dimethyl ether of glycerol, 1,2,6-hexanetriol, trimethylolpropane, methoxyethanol, or a combination comprising one or more of such alcohols.
• alcohols include ethylene glycol, propylene glycol, butyl glycol, glycerol, diethylene glycol, and the like, as well as mixtures thereof.
• the alcohol will be ethylene glycol or 1,2- propylene glycol or 1,3-propylene glycol, while in one exemplary embodiment; the disclosed heat transfer fluid will comprise ethylene glycol.
• the alcohol will be present in the heat transfer fluid in an amount of from 10-99.9% by weight, based on the total amount of the heat transfer fluid.
• the at least one alcohol will be present in the heat transfer fluid in an amount of from 20-99.9% by weight, based on the total amount of the heat transfer fluid, while in one exemplary embodiment, the at least one alcohol will be used in an amount of from 20 to 99.9% by weight, based on the total amount of the heat transfer fluid.
• water may be present in the disclosed corrosion inhibiting heat transfer fluids. In one exemplary embodiment, deionized water will be used.
• water will be present in the corrosion inhibiting heat transfer fluid in an amount of from 0.1-90% by weight, based on the total amount of the heat transfer fluid. In another embodiment, water will be present in the heat transfer fluid in an amount of from 0.1-80% by weight, based on the total amount of the heat transfer fluid, while in one exemplary embodiment, water will be used in an amount of from 0.1 to 70% by weight, based on the total amount of the corrosion inhibiting heat transfer fluid.
• water may not be present in the concentrate version of a heat transfer fluid at all, i.e., 0 wt% but may be present in some concentrates in amounts up to about 50 wt % while in other embodiments water may be present in a concentrate in an amount up to about 20 wt %.
• water may be present in amounts of from 20 wt% up to 90% wt.
• Suitable optional corrosion inhibitors include aluminum and aluminum based alloy corrosion inhibitors, copper and copper based alloy corrosion inhibitors, ferrous metal corrosion inhibitors, amines such as ethanolamine, diethanol amines, triethanolamine, octylamine and morpholine, orthosilicate ester as described in US2004/0028971 Al and the like.
• one or more optional corrosion inhibitors will be present in the heat transfer fluid in an amount of from 0.0 to 10.0 % by weight, based on the total amount of the heat transfer fluid.
• one or more corrosion inhibitors will be present in the heat transfer fluid in an amount of from 0.0-5% by weight, based on the total amount of the heat transfer fluid.
• Suitable heat transfer fluids may also comprise additional additives such as defoamers, surfactants, scale inhibitors, dispersants, wetting agents, bittering agents, and the like, as well as combinations thereof, in amounts of up to 10 % by weight, based on the total amount of the heat transfer fluid.
• suitable heat transfer fluids will comprise from 20-99.9% by weight of at least one alcohol or an alcohol mixture, from 0.1-80% by weigh of water, and from 0.0001 to 0.1 % by weight of a non-conductive colorant, based on the total amount of the heat transfer fluid, and 0.0 to 10% by weight of other optional heat transfer fluid additives.
• the disclosed fuel cell heat transfer fluids will comprise from 20-99.9% by weight of at least one alcohol or an alcohol mixture, from 0.1-80% by weigh of water, and from 0.0001 to 0.1 % by weight of a non-conductive colorant, and 0.0 to 10% by weight of other heat transfer fluid additives based on the total amount of the heat transfer fluid.
• suitable heat transfer fluids will comprise from 20-99.9% by weight of at least one alcohol, from 0.1-80% by weigh of water, from 0 to 5% by weight of one or more corrosion inhibitors, and from 0.0001 to 0.1 % by weight of a non-conductive colorant and an optional antifoam agent in an amount of from 0.0 to 0.1% by weight, based on the total amount of the heat transfer fluid.
• the disclosed heat transfer fluids may be prepared by mixing the components together. Normally, the alcohol and water are preferably mixed together first. The other additives are then added to the alcohol-water mixture by mixing and adequate stirring.
• the disclosed pre-treated ion exchange resins are advantageous in that they are capable of removing ionic species from a treatment solution or heat transfer fluid, maintaining low conductivity in a heat transfer fluid and providing a beneficial property such as color to a heat transfer fluid.
• the disclosed pre-treated ion exchange resins are also advantageous in that they are capable of simultaneously removing ionic species from a heat transfer fluid, maintaining low conductivity in a heat transfer fluid and providing a beneficial property such as color to a corrosion inhibiting heat transfer fluid.
• the effect of mixed bed ion exchange resins upon conductivity in a fuel cell system was evaluated.
• the tests were conducted in a simulated fuel cell stack with a heat transfer system.
• the test unit contains a simulated fuel cell stack with alternating silicone gasket and stainless steel plate stack one above another to simulate a fi ⁇ el cell stack.
• the stack simulated 50 cells connected in series. During the tests, 50 to 60 volts DC were applied across the simulated stack.
• the test unit also contains a heat transfer fluid tank, coupon holders, flow and pressure meters, an electrical heater, a pump, pH, temperature and conductivity sensors, etc. to simulate a fuel cell heat transfer system.
• the outputs from the sensors were recorded by a computer controlled data acquisition system.
• the data resulting from the tests is shown in the following Figures 2, 3, 4, and 5. It can be seen that mixed bed ion exchange resins are required for maintaining a fuel cell heat transfer fluid conductivity lower than 4 ⁇ S/cm for operation longer than several hours.
• BZT was removed by mixed bed ion exchange resin during prolonged contact. lOgrams of a Dow mixed bed resin were added into three glass beakers each containing 1000ml, 500ml and 250ml BZT containing 50% ethylene glycol solution. The BZT concentration was determined to be 1284ppm. The solutions were agitated via a Teflon-coated magnetic stirring bar. The conductivity and the BZT concentrations were measured before and after 22 hours exposure with the resin. The results are shown in the Table 1 below. One can see that BZT is removed by mixed bed resin from the solution. Conductivity of the solutions was also reduced after the treatment with the ion exchange resin.
• Example 2 in reducing conductivity in fuel cell heat transfer fluids contaminated with ionic species was evaluated as set forth in Table 2.
• ionic species e.g., 30ppm NaCl
• the heat transfer fluid was an aqueous solution of 50% vol EG + lOOppm Cl at 80 0 C. Note: BZT was exchanged in 100ml 50% EG solution with 30ppm NaCl.
• Mass loss for the aluminum and brass are set forth below as well as the appearance of the aluminum coupons and the initial and final conductivity of the sample heat transfer fluids.

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